JP6816009B2 - Composition for containers used at low temperatures - Google Patents

Description

Embodiments relate to modifiers used in compositions for forming containers such as freezing containers that are highly transparent and used at low temperatures.

Research is ongoing on polyolefin-based materials for forming freezing containers for use at low temperatures (ie, less than 0 ° C) with high transparency (ie, greater than 95%). For example, the use of propylene-based random copolymers (RCPs) or propylene-based impact copolymers (ICPs) with improved impact resistance with elastomers has been proposed. However, although these random copolymers can provide the desired toughness and transparency for many applications, they are slightly inferior in impact properties at low temperatures compared to polypropylene impact copolymers. In addition, copolymers with improved impact resistance are slightly less transparent than random copolymers. Therefore, there is a long-awaited composition that can provide both toughness and transparency even at low temperatures.

The embodiment can be realized by providing a composition for forming a container to be used at a temperature lower than the ambient temperature, the composition comprising 12% to 30% by weight of the modifier and 230% by weight. Includes 70% to 88% by weight propylene polymer base with a melt flow rate of 2 g / 10 min to 100 g / 10 min according to ASTM D 1238 at ° C./2.16 kg. The modifiers are (a) 20% to 40% by weight block composites based on the total weight of the modifiers, (i) ethylene-propylene copolymers, (ii) isotactic polypropylene polymers, and , (Iii) A block copolymer containing an ethylene-propylene soft block having the same composition as the ethylene-propylene polymer and an isotactic polypropylene hard block having the same composition as the isotactic polypropylene polymer, wherein the soft block is soft. Blocks contain 50% to 80% by weight of ethylene based on the total weight of the blocks and block copolymers contain 20% to 50% by weight of hard blocks based on the total weight of the block polymers. derived from at least one of olefin, - the complex, there are ethylene and C ₃ -C ₁₀ alpha and 40 wt% to 60 wt% of a polyolefin copolymer based on the total weight of (b) modifiers according ASTM D1238 at 190 ° C. / 2.16 kg, a density of 100 g / 10 min ~1500g / 10 min melt index, and ^{0.860g / cm 3 ~0.900g / cm 3} , and a polyolefin copolymer, (c ) Optionally, a first additional copolymer having a refractive index of 1.490 to 1.510, from 0% to 30% by weight, and at least of propylene and ethylene and butene, which are compatible with polypropylene. Includes at least one of the second additional copolymers derived from one.

The features of these embodiments will be readily apparent to those skilled in the art by reference to the accompanying drawings.

It is a figure which shows the DSC melting point temperature profile of the block composite used in the 1st and 2nd modifiers of Examples 1-6. It is a figure which shows the form of the comparative example B at 5 μm and 1 μm. It is a figure which shows the form of the comparative example C in 5 μm and 1 μm. It is a figure which shows the embodiment of Example 1 in 5 μm and 1 μm. It is a figure which shows the embodiment of Example 2 in 5 μm and 1 μm. It is a figure which shows the embodiment of Example 3 in 5 μm and 1 μm.

Transparency can be an issue when blending ethylene-based elastomers with polypropylene. For example, certain elastomers significantly reduce the modulus and transparency of polypropylene. As described above, in order to obtain a transparent composition, for example, by reducing the rubber domain size, it has been proposed to adjust the refractive index of the material in order to avoid scattering of visible wavelengths of light. However, in the method that relies only on the preparation of the refractive index of the elastomer containing polypropylene, there are restrictions on the use of plastomers (such as plastomers having a density exceeding 0.900 g / cm ³ ), and specifically, the impact characteristics at low temperatures are limited. There is also the inconvenience of becoming weaker. Therefore, a new compatibilization method has been proposed in response to particle sizing by compatibilization of a non-refractive index matched elastomer with polypropylene, which is 0.850 g / cm ^{3 to} 0.900 cm ³ (eg 0). .850g ^/ cm 3 to permit the expansion of the elastomer of the applications having a density of ～0.890Cm ³ and / or ^{0.850g / cm 3 ~0.870g / cm 3} ), also low temperature (relatively low temperature of the glass It has relatively good impact characteristics at the transition temperature).

According to embodiments, modifiers for use with a propylene polymer base for forming compositions that form containers for use at low temperatures with high transparency, such as freezer containers, have been proposed. This modifier can increase toughness at low temperatures (ie, less than 0 ° C.) while forming containers with high transparency (ie, greater than 95% transparency). For this modifier, the impact efficiency of the elastomer modifier is directly related to the crystallinity of the modifier and the dispersion of the individual elastomer domains in the polypropylene matrix. Further, conventionally, dispersion of an elastomer with respect to polypropylene has been a problem from the viewpoint of, for example, a melt mixing process and compatibility. Thus, embodiments include impact resistance imparting agents to improve toughness at low temperatures, melt flow improvers to allow good melt mixing, and optionally 1.490 to 1.510 (. For example, a modifier combined with a transparency-imparting agent having a refractive index (similar to the refractive index of polypropylene homopolymers) and / or miscibility with polypropylene (eg, miscibility with polypropylene homopolymers). It relates to a modifier which is a material well known to those skilled in the art. For example, the modifier is provided in a pre-blended form as a single component (eg, in pellet form) and is used in existing processes that use at least a propylene polymer base to form containers such as freezer containers. Can be added. As will be appreciated by those skilled in the art, this modifier can be added as a separate component to the propylene polymer base, even if it is not commercially efficient and / or preferred.

The term "composition" and similar terms mean a mixture or blend of two or more components. For example, one composition is a combination of a random or propylene-based polymer and a block composite.

The terms "blend", "polymer blend" and similar terms mean a blend of two or more polymers. Such blends may or may not be miscible. Such blends may or may not be phase separated. Such blends may or may not contain one or more domain configurations determined by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods well known in the art. You may.

"Polymer" means a compound prepared by polymerization of the same or different types of monomers. As a generic term, polymers therefore include the term homopolymer, which is usually used to refer to polymers prepared from only one type of monomer, and the term interpolymer, as defined below. It also includes all forms of interpolymers such as random, block, uniform, non-uniform and the like. The terms "ethylene / alpha-olefin polymer" and "propylene / alpha-olefin polymer" refer to the interpolymers described below.

"Interpolymer" and "copolymer" mean a polymer prepared by the polymerization of at least two different types of monomers. These generic terms include both classical copolymers, that is, polymers prepared from two different types of monomers and polymers prepared from two or more different types of monomers, such as terpolymers, tetrapolymers, etc. Including.

"Propylene-based polymers" and similar terms include, with the majority of the weight percent containing polymerized propylene monomers (based on the total weight of the polymerizable monomers), optionally forming propylene-based interpolymers. It means a polymer containing at least one polymerized comonomer different from propylene. For example, when the propylene-based polymer is a copolymer, the amount of propylene exceeds 50% by weight based on the total weight of the copolymer. "Units derived from propylene" and similar terms mean units of polymers formed from the polymerization of propylene monomers. "Units derived from alpha-olefins" and similar terms refer to units of polymers formed from at least one polymerization of alpha-olefin monomers, specifically C _3-10 alpha-olefins. In contrast, "ethylene-based polymers" and similar terms include mostly polymerized ethylene monomers (based on the total weight of polymerizable monomers) and optionally include ethylene-based interpolymers. It means a polymer that can contain at least one polymerized comonomer that is different from ethylene to form. For example, when the ethylene-based polymer is a copolymer, the amount of ethylene exceeds 50% by weight based on the total weight of the copolymer.

"Random propylene-based interpolymers" and similar terms are polymer chains, as opposed to units derived from alpha-olefin monomers distributed across the polymer chains in alternating, periodic, or block patterns. Means a propylene / alpha-olefin interpolymer that is randomly distributed over. An exemplary random propylene interpolymer is a random propylene copolymer. In contrast, "homogeneous propylene-based interpolymers" and similar terms are propylene / alpha-olefin interpolymers in which units derived from alpha-olefin monomers are randomly and approximately uniformly distributed across the polymer chains of the bulk polymer. Means that.

"Propene-based copolymers with improved impact resistance" and similar terms have a composition as compared to the notched isod impact strength of a given composition obtained at the same temperature without the use of impact resistance improvers. Notched Izod means a propylene-based polymer composition whose impact resistance has been improved so that the impact strength is maintained below room temperature or enhanced.

The term "block composite" and similar terms are meant to include soft copolymers, hard polymers, and block copolymers having soft segments / blocks and hard segments / blocks, where the hard segments of block copolymers are block composites. It has essentially the same composition as the hard polymer of, and the soft segment of the block copolymer has essentially the same composition as the soft copolymer in the block composite. Specifically, the block composite comprises a hard polymer containing polypropylene and a soft polymer containing ethylene (as an ethylene propylene polymer).

A "block copolymer" is a polymer that contains two or more chemically distinct regions or segments (also known as "blocks") that are linearly bonded, i.e. a polymerized functional rather than a pendant or grafted mode. In terms of sex (eg, polymerized propylene functionality), it means a polymer containing chemically distinct units bonded (covalently) from end to end. Block copolymers include sequences of the same monomeric units (“blocks”) that are covalently attached to different types of sequences. These blocks can be connected in various ways, such as diblocks such as AB and ABA triblock structures, where A represents one block and B represents different blocks in the equation. ing. In multi-block copolymers, A and B are linked in many different ways and can be repeated multiple times. It may further contain additional blocks of different types. Multi-block copolymers can be linear multi-blocks, multi-block star polymers (all blocks bonded to the same atom or chemical composition), or comb-like polymers with B blocks bonded to the A backbone at one end. .. The block copolymer can be linear or branched. For this block copolymer, the blocks may differ in the amount of comonomer incorporated therein. The blocks are composed of comonomer type, density, amount of crystallinity, microcrystal size due to the polymer of such composition, type or degree of stereoregularity (isotactic or syndiotactic), positional regularity or It differs in position irregularity, amount of branching, including long or hyperbranching, uniformity, and / or any other chemical or physical property. Block copolymers are unique based on polymer polydispersity (PDI or M _w / M _n ), block length distribution, and / or, for example, the effect of one or more shutling agents in combination with one or more catalysts. It may be characterized by a distribution of block numbers.

A "hard" segment / block refers to a highly crystalline block of polymerization units. The term "soft" segment / block refers to a block of non-crystalline, substantially non-crystalline, or elastomeric units of polymerization. The term "crystallinity" refers to a polymer or polymer block having a primary transition or crystal melting point ( _Tm ) as determined by differential scanning calorimetry (DSC) or equivalent techniques. This term can be used interchangeably with the term "semi-crystalline". The term "crystallinity" means a monomer that can polymerize such that the resulting polymer is crystalline. The crystalline propylene polymer can have a density of 0.88 g / cc to 0.91 g / cc and a melting point of 100 ° C. to 170 ° C., but is not limited thereto. The term "non-crystalline" means a polymer that lacks a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent techniques.

The term "isotactic" is defined as a polymer repeating unit with at least 70 percent isotactic pentad, as determined by ¹³ C-NMR analysis. "Highly isotactic" is defined as a polymer with at least 90 percent isotactic pentad.

Compositions According to embodiments, compositions for forming highly transparent, low temperature containers containing at least a propylene polymer base and modifiers, and containers / films formed using the compositions. .. High Transparency-Containers used at low temperatures form a relatively transparent film (eg, less than 5.0 mm thick) with at least 95% transparency and at least at a low temperature of -20 ° C. It means a container formed by using a composition exhibiting an Izod impact of 5 kJ / m ² . For example, as an isod impact at -20 ° C, 5kJ / m ^{2 to} 75kJ / m ² , 5kJ / m ^{2 to} 55kJ / m ² , 5kJ / m ^{2 to} 45kJ / m ² , 5kJ / m ^{2 to} 40kJ / m ² , 6 kJ / m ^{2 to} 35 kJ / m ² , and / or 9 kJ / m ^{2 to} 35 kJ / m ² . The film for forming the container has a thickness of less than 5.0 mm, less than 4.0 mm, and / or less than 3.0 mm. For example, the thickness may be 0.1 mm to 4.5 mm, 0.2 mm to 4.0 mm, 0.5 mm to 3.0 mm, and / or 0.5 mm to 2.0 mm.

The composition comprises 12% to 30% by weight of the modifier based on the total weight of the composition. For example, the amount of modifier is 15% to 30% by weight, 18% to 28% by weight, 19% to 25% by weight, and / or 18% to 22% by weight. Block composites, polyolefin copolymers, and optionally additional copolymers of modifiers, prior to blending the modifiers with the propylene polymer base so that the composition comprises a modifier finely dispersed in polypropylene. Can be pre-blended. In another exemplary embodiment, the components of the modifier blend, together with the modifier blend components, supply a propylene polymer base to the extruder in one step to form modified propylene in the preparation of the article. Can be added individually. In another exemplary embodiment, modified propylene is prepared by melt-blending all of the individual components of the modifier blend with a propylene polymer base and then pelletizing ready-to-feed modified propylene. obtain. The pelletized modified propylene can then be fed directly into the process for the article, for example by injection molding.

The modifier comprises a block composite containing a block copolymer in 20% to 40% by weight (eg, 25% to 35% by weight and / or 28% to 32% by weight). The block complex may include one or more block complexes. The modifier is 40 to 60% by weight (for example, 45% to 55% by weight and / or 48% to 52% by weight) of a polyolefin copolymer having a relatively high melt flow rate and a relatively low density. ) Included. Polyolefin copolymers may include one or more polyolefin copolymers having a relatively high melt flow rate and a relatively low density. The modifier may optionally be at least one additional copolymer from 0% to 30% by weight (eg, 10% to 30% by weight, 15% to 25% by weight, and / or 18% by weight to. 22% by weight). Additional copolymers can have a refractive index similar to polypropylene homopolymers, specifically 1.490 to 1.510, and / or additional copolymers are compatible with polypropylene. (And derived from propylene and ethylene and / or butene). Additional copolymers may include one or more copolymers having a refractive index similar to that of polypropylene homopolymers.

Although not bound by this theory with respect to compositions, blending propylene polymer bases (eg, polypropylene homopolymers, etc.) with block copolymers having a continuous polypropylene phase is a simple polypropylene / elastomer blend. In comparison, it is thought to result in relatively small and discrete rubber domains. When the domain size of the rubber is smaller than the wavelength of visible light (400-700 nm), there is less light scattering and the polymer / resulting article can maintain transparency. In addition, block copolymers are rubber so that the propylene polymer base can be considered to have undergone impact-resistant modification with improved toughness at low temperatures, such as the temperature in a typical freezer. To be compatible with each other. Thus, the resulting composition may have improved impact resistance modifications while at the same time having a light transmittance similar to that achieved with polypropylene homopolymers. For example, the modifier is a composition suitable for forming articles that are immediately compatible and dispersible in polypropylene, transparent in polypropylene, and exhibit sufficient impact strength at the temperature in the freezer. Can have features that bring about.

For example, a film formed using a modifier composition and a propylene polymer base is at −20 ° C. the same propylene polymer base (such as a clear polypropylene random copolymer and / or polypropylene homopolymer) and / or Can show improved average izod than films formed using polypropylene impact copolymers alone (formed at the same thickness and under the same conditions). For example, if the composition contains 25% by weight modifier, the average izod at -20 ° C can be improved by at least 10-fold compared to using only the clear polypropylene random copolymer. , Can be improved by at least 3 times compared to using only polypropylene impact copolymer. When the composition contains 20% by weight modifier, the average izod at -20 ° C can be improved by at least 6-fold compared to using only the clear polypropylene random copolymer, and polypropylene. It can be improved by at least 1.2 times compared to using only the impact copolymer. When the composition contains 15% by weight of the modifier, the average izod at -20 ° C can be improved by at least 3-fold compared to using only the clear polypropylene random copolymer. Therefore, if the composition contains a modifier, an improvement in average izod at −20 ° C. can be expected.

Films formed using the modifier composition and the propylene polymer base were formed using only the propylene polymer base (eg, clear polypropylene random copolymers) (at the same thickness and under the same conditions). Can exhibit good transparency at least as good as the film (formed in). Therefore, by using a modifier, transparency similar to that of a transparent polypropylene random copolymer can be achieved. Transparency can also be improved for polypropylene impact copolymers.

Films formed using the modifier composition and the propylene polymer base are at least films formed using only polypropylene impact copolymers (formed at the same thickness and under the same conditions). It can show a three-fold improved haze rate. When the comparative film is formed using only the clear polypropylene random copolymer, the haze rate can show similar values (eg, within ± 20%).

Films formed using the modifier composition and the propylene polymer base are more than films formed using only polypropylene impact copolymers (formed at the same thickness and under the same conditions). Can show improved permeability. When the comparative film is formed using only the clear polypropylene random copolymer, the transmittance can show similar values (eg, within ± 15%).

Films formed using the modifier composition and the propylene polymer base are more than films formed using only transparent polypropylene impact copolymers (formed to the same thickness and under the same conditions). Can show at least as good transparency. When the comparative film is formed using only polypropylene impact copolymers, the transparency can be improved by at least 10 times (eg, at least 10 times better).

Polymer blends are made by known polymer methods such as extrusion (eg sheet extrusion and profile extrusion), casting (eg injection molding, rotation molding, and blow molding), and inflation film and cast film processes. It may be used to prepare the container. For example, extrusion is typically a process in which a polymer is continuously propelled along a screw through a hot and high pressure region where the polymer is melted, compressed, and finally extruded through a mold. The extruder can be a single-screw extruder, a multi-screw extruder, a disc extruder, or a ram extruder. The mold can be a film mold, an inflation film mold, a sheet mold, a pipe mold, a pipe mold, or a profile extrusion mold. Injection molding is widely used to manufacture a variety of plastic parts for a variety of applications. Typically, injection molding is the process by which a polymer is melted and injected at high pressure into a mold that is the reverse of the desired shape to form a part of the desired shape and size. The mold can be made of metal such as steel and aluminum. Casting is typically the step in which the polymer is melted and guided into a mold that is the reverse of the desired shape to form a part of the desired shape and size. The casting can be unpressurized or pressure utilization casting. In an exemplary embodiment, the container is prepared using injection molding.

The temperature at which the polymer blend of the modifier and the propylene polymer base is formed may be higher than the melting temperature of the propylene polymer base. For example, the temperature can be between 150 ° C. and 250 ° C. and / or 200 ° C. and 225 ° C. to form a uniform melt blend. The temperature for forming the modifier can be 150 ° C to 200 ° C when pre-blended. For example, the temperature for pre-blending the modifier may be lower than the temperature for forming the polymer blend of the modifier and the propylene polymer base. The polymer blend of the modifier and the propylene polymer base may have a relatively low viscosity blend (compared to conventional modifiers in polypropylene) or may operate at even lower temperatures. , May operate in shorter cycle times, and / or may provide a homogeneous blend with an improved balance of clarity and impact properties.

Block Composites In embodiments, the block composites are (i) ethylene-propylene copolymers (also known as soft polymers), (ii) isotactic polypropylene polymers (also known as hard polymers), and (iii) ethylene-propylene polymers. Includes a block copolymer containing an ethylene-propylene soft block (also known as EP soft block) having the same composition as the above and an isotactic polypropylene hard block (also known as iPP hard block) having the same composition as the isotactic polypropylene polymer. With respect to block copolymers, soft blocks are 50% to 80% by weight (eg, 55% to 75% by weight, 60% to 70% by weight, and / or 63% by weight, based on the total weight of the soft block. ~ 68% by weight) of ethylene, the remainder of the soft block is propylene. Hard blocks of block copolymers contain less than 5% by weight and / or less than 4.5% by weight ethylene and, optionally, the rest of isotactic polypropylene having a similar composition of more than 0.5% by weight. Including. For example, a hard block may contain from 1.5% to 4.1% by weight ethylene and / or 2.1% to 3.5% by weight ethylene based on the total weight of the block copolymer. In addition, block copolymers contain 20% to 50% by weight of hard blocks (eg, 20% to 40% by weight, 25% to 35% by weight, and / or 28% to 32% by weight). The remainder is a soft block.

The iPP-EP block copolymers in block composite polypropylene-based olefin block copolymers containing iPP hard blocks and ethylene-propylene soft blocks have the domain size of the elastomeric phase (eg, modifiers) when blended with propylene polymers. For example, a compatibilizing solution is provided that reduces (so that it falls within the range of 100 nm to 500 nm). This forms a compatible blend of polypropylene and elastomer, providing a wide range of thermodynamically stable compositions with finer morphology than those achievable with conventional blends, resulting in , Brings a combination of unique properties.

The melting temperature of the block composite can be 110 ° C to 130 ° C (eg, 115 ° C to 125 ° C). At a melting temperature of 110 ° C., the ethylene content in the hard block is estimated to be about 4.0% by weight, and at 130 ° C., the ethylene content in the hard block is estimated to be about 1.6% by weight. It is estimated that at a melting temperature of 115 ° C., the ethylene content in the hard block is about 3.4% by weight and at 125 ° C., the ethylene content in the hard block is about 2.2% by weight. The total ethylene content in the block composite is 25% to 70% by weight (eg, 30% to 60% by weight, 35% to 55% by weight, 40% by weight) based on the total weight of the block composite. ~ 50% by weight, etc.).

In other words, a hard segment of a block copolymer is a highly crystalline unit of polymerization in which the monomer (ie, isotactic polypropylene) is present in an amount greater than 95% by weight and / or more than 98% by weight. Refers to the block shown. The soft segment comprises 50% to 80% by weight of comonomer (ie, ethylene) and less than 50% by weight of monomer (ie, propylene). For example, the soft segment means an amorphous, substantially amorphous, or elastomeric block of polymerization units having a comonomer content greater than 10 mol%. The weight percent of the hard segment in the block copolymer can be 5% to 95% by weight (the remainder is the soft segment). The molecular weight of block copolymers can be 50,000 to 1,000,000 g / mol.

Block copolymers are characterized by having a block complex index of 0.1 or more and 1 or less. For example, the block complex index is 0.1-0.9, 0.1-0.8, 0.1-0.7, 0.1-0.6, 0.1-0.5, 0. It can be 1 to 0.4, 0.1 to 0.3, 0.1 to 0.2, and the like. Block copolymers are characterized as having a molecular weight distribution of M _W / _MN greater than about 1.3. For example, M _w / M _n can be 1.4 to 5.0, 1.7 to 3.5, and / or 1.7 to 2.5.

The block composite may have a melt flow rate of 2 g / 10 min to 100 g / 10 min according to ASTM D 1238 at 230 ° C./2.16 kg. For example, the melt flow rate is 2 g / 10 min to 50 g / 10 min, 2 g / 10 min to 30 g / 10 min, 2 g / 10 min to 25 g / 10 min, 2 g / 10 min to 20 g / 10 min, 2 g / 10 Minutes to 15 g / 10 minutes, 3 g / 10 minutes to 10 g / 10 minutes, and / or 4 g / 10 minutes to 7 g / 10 minutes. The melt flow rate of the block composite may be less than the melt index (based on g / 10 min according to ASTM D1238 at 190 ° C./2.16 kg) of the polyolefin copolymer contained in the modifier.

Block complexes include block copolymers with the most probable block length distribution. Block copolymers can include two or three blocks or segments. In the method of producing a polymer of a block composite, multiple reactors operated under plug flow conditions in the form of a polymer substantially terminated with a chain shuttling agent as a means of extending the life of the polymer chains. At least in the first reactor, or in the first zone of the multi-partitioned reactor, a substantial portion of the polymer chain is ejected and polymerization conditions with different polymer chains are experienced in the next reactor or polymerization compartment. As such, chain shuttling is used as a means of extending the life of polymer chains.

Different polymerization conditions in each reactor or zone can be different monomers, comonomer, or monomer / comonomer ratios, different polymerization temperatures, different monomer pressures or partial pressures, different catalysts, different monomer gradients, or identifiable polymers. Includes the use of any other difference that leads to the formation of segments. Thus, at least a portion of the polymer comprises two, three, or more, preferably two or three differentiated polymer segments located within the molecule.

The block composite polymer is, for example, contacting a composition comprising an addition polymerization catalyst, a cocatalyst, and at least one of a chain shuttling agent under addition polymerization conditions, for example, an addition-polymerizable monomer or a mixture of monomers. Prepared by a process involving letting. This process grows under distinct step conditions within two or more reactors operating under steady-state polymerization conditions, or within two or more zones of reactors operating under plug-flow polymerization conditions. It is characterized by the formation of at least some of the polymer chains.

Suitable methods useful in producing block complexes can be found, for example, in US Pat. Nos. 8,053,529, 8,686,087, and 8,716,400. The polymerization is a continuous polymerization, eg, a catalyst component, a monomer, and optionally a solvent, an adjuvant, a scavenger, and / or a polymerization aid, which is continuously supplied to one or more reactors or zones to produce a polymer. It can be carried out as a continuous solution polymerization in which the material is continuously removed from it. Within the terms "continuous" and "continuously" used in this context, there are intermittent additions of reactants and removal of products at small regular or irregular intervals, with time. With the passage of time, the whole process is substantially continuous. In addition, the first reactor or zone, shortly before the outlet or outlet of the first reactor, between the first reactor or zone and the second or any subsequent reactor or zone, or alone. Chain shuttling agents can be added at any time during the polymerization, including a second or any subsequent reactor or zone in. Exemplary chain shuttling agents, catalysts, and co-catalysts are disclosed, for example, in US Pat. No. 7,951,882. For example, chain shuttling agents that are dialkylzinc compounds can be used.

The catalyst can be prepared as a homogeneous composition by adding the required metal complex or multiple complexes to a suitable diluent for the solvent or final reaction mixture to be polymerized. The desired co-catalyst or activator and, optionally, the shutting agent may be either before, simultaneously or after combining the catalyst with the monomer to be polymerized and any additional reaction diluent. , Can be combined with the catalyst composition.

Conmonomer content, crystallinity, density within the same molecule due to differences in monomer, temperature, pressure, or other differences in polymerization conditions between at least two reactors or zones connected in series. Polymer segments of different compositions, such as stereoregularity, positional regularity, or other chemical or physical differences, are formed in different reactors or zones. The size of each segment or block is determined by the continuous polymer reaction conditions and is preferably the most likely distribution of polymer size. Each of the series of reactors can be operated under high pressure, solution, slurry, or gas phase polymerization conditions.

In the following exemplary process, continuous or substantially continuous polymerization conditions can be used. In multi-zone polymerization, all zones are the same type of polymerization, such as solutions, slurries, or vapor phases, but are operated under different process conditions. For solution polymerization processes, it is desirable to use a homogeneous dispersion of catalyst components in a liquid diluent in which the polymer is soluble under the polymerization conditions used. The high pressure process can be carried out at temperatures between 100 ° C. and 400 ° C. and pressures above 500 bar (50 MPa). The slurry process may use an inert hydrocarbon diluent and, from 0 ° C. to the most recent temperature at which the polymer is substantially soluble in the inert polymerization medium. The temperature in the exemplary slurry polymerization is from 30 ° C. and the pressure is in the range of atmospheric pressure (100 kPa) to 500 psi (3.4 MPa).

Although not intended to limit the scope of the embodiments, one means for carrying out such a polymerization process is as follows. In one or more well-stirred tank or loop reactors operated under solution polymerization conditions, the monomer to be polymerized is continuously introduced in a portion of the reactor with any solvent or diluent. The reactor contains a relatively homogeneous liquid phase consisting of substantially monomers, along with any solvent or diluent and dissolved polymer. Exemplary solvents include C _4-10 hydrocarbons or mixtures thereof, specifically alkanes such as mixtures of hexanes or alkanes, and one or more monomers used for polymerization. A co-catalyst, and optionally a catalyst with a chain shuttling agent, is continuously or intermittently introduced into the reactor liquid phase or its recycled portion at at least one location.

Reactor temperature and pressure can be adjusted by solvent / monomer ratio, catalyst addition rate, and the use of cooling and / or heating coils, jackets, or both. The polymerization rate is controlled by the catalyst addition rate. The content of a given monomer in the polymer product is affected by the ratio of the monomers in the reactor, which is controlled by manipulating the rate of supply of each of these components to the reactor. The molecular weight of the polymer product is optionally controlled by controlling other polymerization variables such as temperature, monomer concentration, or the chain shuttling agent described above, or a chain terminator such as hydrogen. Optionally, by a conduit or other means of transfer of the reactor, the reaction mixture prepared in the first reactor is expelled into the second reactor without substantially stopping polymer growth. A second reactor is connected to the outlet. Differences in at least one process condition are established between the first and second reactors. For example, the difference in use in the formation of a copolymer of two or more monomers is the presence or absence of one or more comomers or the difference in comonomer concentration. Individual additional reactors may be provided that are arranged similarly to a series of second reactors. Upon discharge from the final reactor in a series of reactors, the effluent is brought into contact with a catalytic deactivator, such as water, water vapor, or alcohol, or with a coupling agent. The resulting polymer product is recovered by evaporating and separating the volatile components of the reaction mixture, such as residual monomers or diluents, under reduced pressure and, if necessary, further liquefying in equipment such as a liquefaction extruder. To.

Alternatively, the polymerization described above uses monomers, catalysts, shutling agents, temperatures or other gradients established between different zones or regions, optionally with the addition of catalysts and / or chain shutling agents. And it can be carried out in a plug flow reactor operated under adiabatic or non-adiabatic polymerization conditions.

High Melt Flow Polyolefin Copolymers In embodiments, the polyolefin copolymers are derived from ethylene and at least one of the C _{3 to} C ₁₀ alpha-olefins, or propylene and C ₂ and C _{4 to} C ₁₀ Derived from at least one of the alpha-olefins. For example, the polyolefin copolymer can be an ethylene-propylene copolymer, an ethylene-butylene copolymer, and / or an ethylene-octene copolymer. The polyolefin copolymer has a relatively high melt index such that the melt index is 100 g / 10 min to 2000 g / 10 min according to ASTM D1238 at 190 ° C./2.16 kg. For example, the melt index is 100 g / 10 min to 1500 g / 10 min, 200 g / 10 min to 1200 g / 10 min, 300 g / 10 min to 700 g / 10 min, and / or 400 g / 10 min to 600 g / 10 min. possible. Polyolefin copolymers, according to ASTM D792, has a relatively low density such that the density is ^{0.860g / cm 3 ~0.900g / cm 3} . For example, the densities are 0.860 g / cm ^{3 to} 0.890 g / cm ³ , 0.860 g / cm ^{3 to} 0.885 g / cm ³ , 0.865 g / cm ^{3 to} 0.880 g / cm ³ , 0.870 g. It can be / cm ^{3 to} 0.879 g / cm ³ and / or 0.872 g / cm ^{3 to} 0.876 g / cm ³ .

Polyolefin copolymers can have low glass transition temperatures, such as below -30 ° C, below -40 ° C, and / or <-50 ° C. The glass transition temperature (T _g ) may be higher than −80 ° C. Brookfield viscosities (at 350 ° F./177 ° F.) are 1,000 cP to 25,000 cP (eg, 3,000 cP to 20,000 cP, 5,000 cP to 20,000 cP, 10,000 cP to 20,000 cP, and / Alternatively, it can be between 15,000 cP and 20,000 cP).

Polyolefin copolymers, 40,000 g / mol, 30,000 g / mol or less, and / or may have a low weight average molecular weight of such 25,000 g / mol or less _{(M W).} The weight average molecular weight _{(M W)} is, 5000 g / mol, 7000 g / mol, and / or may be 10,000 g / mol or more.

Additional Polyolefin Copolymers In embodiments, additional copolymers, if present, may include a first additional copolymer and / or a second additional copolymer. The first additional copolymer has a refractive index of 1.490 to 1.510, as will be appreciated by those skilled in the art. First additional copolymer, C ₂ -C ₁₀ alpha - at least two copolymers of olefins, and / or may comprise a copolymer derived from at least styrene. The first additional copolymer is derived from at least two selected from ethylene, propylene, butylene, pentene, hexene, heptene, and octene (ie, two or more selected from those listed below). It can be a copolymer to be produced, or it can be a styrene-based copolymer. For example, the first additional copolymer can be derived from at least two of ethylene, propylene, and butylene, or can be a styrene-based copolymer. For example, additional copolymers may include ethylene-propylene copolymers and / or ethylene-butylene copolymers. The second additional copolymer is miscible with polypropylene and is derived from at least one of propylene and ethylene and butene. For example, the second additional copolymer can be a propylene-ethylene interpolymer or a propylene-ethylene-butene interpolymer.

Exemplary additional copolymers derived from alpha-olefins are available from The Dow Chemical Company under the trade names ENGAGE ™ and VERSIFY ™. As exemplary styrene-based copolymers, Kraton® brands such as the reinforced rubber segments Kraton® G1643M and Kraton® G1645M grades are available from Kraton Performance Polymers.

The propylene polymer base composition comprises 70% by weight to 88% by weight of the propylene polymer base, which is 2 g / 10 min to 100 g / 10 min (eg, according to ASTM D 1238 at 230 ° C./2.16 kg). It has a melt flow rate of 10 g / 10 min to 80 g / 10 min, 20 g / 10 min to 60 g / 10 min, 30 g / 10 min to 50 g / 10 min, and / or 35 g / 10 min to 45 g / 10 min). .. The propylene polymer base may comprise one or more polypropylene-based polymers having a melt flow rate of 2 g / 10 min to 100 g / 10 min according to ASTM D 1238 at 230 ° C./2.16 kg. In an exemplary embodiment, the composition may essentially consist of a modifier and a propylene polymer base. The propylene polymer base may include a random copolymer polypropylene having an ethylene content of 0.5% to 5.0% by weight based on the total weight of the random copolymer polypropylene. The propylene polymer base may include 95% to 100% by weight of random copolymer polypropylene based on the total weight of the propylene polymer base.

As the propylene polymer base, polypropylene in the isotactic form of homopolymer polypropylene and / or polypropylene in other forms (eg, syndiotactic or atactic) can also be used. The propylene polymer base may include an impact copolymer containing a rubber phase dispersed in propylene. Depending on the molecular weight, the melt flow rate of polypropylene used may vary depending on the application. Discussions on various polypropylene polymers include, for example, Modern Plastics Encyclopedia / 89, mid October 1988 Issue, Volume 65, Number 11, pp. It is published in 86-92.

The propylene polymer base may contain a fining agent and / or a nucleating agent inside. For example, finings and / or nucleating agents can change the way polypropylene chains crystallize and aggregate in the molten state. These agents can increase the onset of crystallization temperature. Finings (or purifiers) are usually organic non-polymeric molecules. Finings can generally also act as a nucleating agent, but the nucleating agent does not necessarily have to be a fining agent. An exemplary fining agent is a chemical derivative of dibenzidene sorbitol, which has a melting temperature within a polypropylene resin treatment window. The nucleating agent is generally an inorganic material having a small average particle size and a high melting point. When the nucleated resin is melted in an extruder, the nucleating agent typically remains solid and may provide an environment in which polypropylene spherulites can be formed. An exemplary nucleating agent is a chemical derivative of benzoic acid. For example, the nucleating agent can be sodium benzoate, kaolin, and / or talc.

The composition can be used in the manufacture of durable containers for applications that require low temperature mechanical (eg, below ambient temperature and / or below 0 ° C.). The container may be suitable for use in the food and beverage consumption market. Examples of container-based applications that can benefit from an improved balance of impact, transparency, and modulus are food packaging for low temperature mechanical properties (eg, ice cream containers and puncture resistance bags). Includes beverage bottles and clear, durable luggage bags.

Test Method Density is measured according to ASTM D792. Results are reported in gamma (g) / cubic centimeters, or g / cm ³ .

The melt index (I ₂ ) is measured according to ASTM D-1238 (190 ° C; 2.16 kg). Results are reported in grams / 10 minutes.

Melt flow rate (MFR) is measured according to ASTM D-1238 (230 ° C; 2.16 kg). Results are reported in grams / 10 minutes.

Tensile properties are measured according to ASTM D638, including tensile strength at break and elongation at break.

The second flexural modulus including Flex 1% and Flex 2% is measured according to ASTM D790.

Percent transparency, percent haze, and percent transmittance are measured using the BYK Gardener Haze-gard as defined by ASTM D1746.

Izod impacts at 23 ° C, 0 ° C, and -20 ° C are measured according to ASTM D256 with the thickness shown in each example. Samples are prepared by inductive molding.

Differential scanning calorimetry (DSC) is performed on TA Instruments Q100 DSC V9.8 Building 296 using TA Instruments' Universal V3.7A analysis software. The sample is quickly heated to 230 ° C. and kept isothermal for 3 minutes to erase any previous heating history. The sample is then cooled to −90 ° C. at a rate of 10 ° C./min and held at −90 ° C. for 3 minutes. Record the first cooling curve and the second heating curve. The ratio of crystallinity is calculated by dividing the heat of fusion (H _f ) determined from the second heating curve by the theoretical heat of fusion of 292 J / g (165 J / g for PP) in the case of PE. Is calculated by multiplying by 100 (for example, crystallinity% = (H _f / 292 J / g) × 100 (in the case of PE)).

Specifically, unless otherwise specified, the melting point (T _m ) of each polymer is determined from the second thermal curve (peak T _m ), and the crystallization temperature (T _c ) is determined by the first cooling curve (peak T _c). ) To determine. For DSC, the temperature at maximum flow rate with respect to the linear baseline is used as the melting point. A linear baseline is constructed from the start of melting (above the glass transition temperature) to the end of the melting peak.

High Performance Liquid Chromatography: High Performance Liquid Chromatography Experimental Methods Measurements are performed by published methods (Lee, D .; Miller, MD; Meunier, DM; Lyons, JW; Bonner, J.M. .; Pell, RJ; Shan, CLP; Huang, TJ Chromatogr. A2011, 1218, 7173) is an HTLC experiment performed according to a method with slight modifications. Two Shimadzu (Columbia, MD, USA) LC-20AD pumps are used to deliver decane and trichlorobenzene (TCB), respectively. Each pump is connected to a 10: 1 fixed flow divider (part number: 620-PO20-HS, Analytical Scientific Instruments Inc., CA, USA). Divider has according to the _{manufacturer,} in _H 2 O, the pressure drop of 1500psi at 0.1 mL / min. Set the flow rate of both pumps to 0.115 mL / min. After splitting, for both decane and TCB, the microflow determined by weighing the collected solvent over 30 minutes is 0.01 mL / min. The volume of eluate collected is determined by the mass and density of the solvent at room temperature. A micro flow rate is delivered to the HTLC column for separation. The main flow is sent back to the solvent reservoir. A 50 μL mixer (Shimadzu) is connected after the divider to mix the solvent from the Shimadzu pump. The mixed solvent is then delivered to a syringe in the oven of Waters (Milford, MA, USA) GPCV2000. A Hypercarb ™ column (2.1 × 100 mm, 5 μm particle size) is connected between the injector and a 10-port VICI valve (Houston, TX, USA). The valve comprises two 60 μL sample loops. A valve is used to continuously sample the eluate from the first dimension (D1) HTLC column to the second dimension (D2) SEC column. A Waters GPCV2000 pump and PLgel Rapid ™ -M column (10 x 100 mm, 5 μm particle size) are connected to a VICI valve for D2 size exclusion chromatography (SEC). For the connection, the symmetrical configuration described in the literature (Brun, Y .; Faster, PJ Sep. Sci. 2010, 33, 3501) is used. Double-angle light scattering detectors (PD2040, Agilent, Santa Clara, CA, USA) and IR5 speculative absorption detectors are connected after the SEC column to measure concentration, composition, and molecular weight.

Separation of HTLC: Dissolve about 30 mg in 8 mL decan by gently shaking the vial at 160 ° C. for 2 hours. Decane contains 400 ppm BHT (2,6-di-tert-butyl-4-methylphenol) as a radical scavenger. The sample vial is then moved to the GPCV2000 autosampler for injection. The temperature of both the autosampler, syringe, Hypercarb and PLgel columns, the 10-port VICI valve, and both the LS and IR5 detectors is maintained at 140 ° C. during the separation.

The initial conditions before injection are as follows. The flow rate of the HTLC column is 0.01 mL / min. The solvent composition in the D1 Hypercarb column is 100% decane. The flow rate of the SEC column is 2.51 mL / min at room temperature. The solvent composition on the D2 PLgel column is 100% TCB. The solvent composition on the D2 SEC column does not change during the separation.

A sample solution of 311 μL aliquots is injected into the HTLC column. The infusion causes the gradient described below.
From 0 to 10 minutes, 100% decan / 0% TCB,
From 10 to 651 minutes, the TCB increases linearly from 0% TCB to 80% TCB.
Infusions also include light scattering signals at a 15 ° angle (LS15), as well as "scale" and "methyl" signals (IR _scales and "methyl" signals from IR5 detectors using the EZChrom ™ Chromatography Data System (Agilent). It also causes the collection of IR _methyl ). The analog signal from the detector is converted to a digital signal through the SS420X analog-to-digital converter. The collection frequency is 10 Hz. The injection also causes switching of the 10-port VICI valve. Valve switching is controlled by a relay signal from the SS420X transducer. The valve is switched every 3 minutes. Chromatograms are collected from 0 to 651 minutes. Each chromatogram consists of 651/3 = 217SEC chromatograms.

After gradient separation, 0.2 mL TCB and 0.3 mL decan are used to wash and rebalance the HTLC column for the next separation. The flow rate for this step is 0.2 mL / min and is delivered by a Shimadzu LC-20AB pump connected to the mixer.

Data analysis of HTLC: A 651 minute raw chromatogram is first folded to give a 217SEC chromatogram. Each chromatogram is 0-7.53 mL in 2D elution volume units. The integration limit is then set and the SEC chromatogram undergoes spike removal, baseline correction, and smoothing. This process is similar to batch analysis of multiple SEC chromatograms in conventional SEC. The sum of all SEC chromatograms is visually inspected to ensure that both the left side (upper integration limit) and the right side (lower integration limit) of the peak are at baseline as zero. Otherwise, adjust the integration limit and repeat the process.

Each SEC chromatogram n of 1-217 yields an XY pair in the HTLC chromatogram, where n is a fraction.

In the formula, t _switching = 3 minutes is the switching time of the 10-port VICI valve.

The above equation uses the IR _scale signal as an example. The resulting HTLC chromatogram shows the concentration of distinct polymer components as a function of elution volume. A normalized IR _scale HTLC chromatogram is shown, for example, in FIG. 9, where Y is represented by dW / dV, which means a normalized weight fraction with respect to elution volume.

The XY pairs of data are also obtained from the IR _methyl signal and the LS15 signal. The calibrated composition is calculated using the IR _methyl / IR _scale ratio. The weight average molecular weight (Mw) after calibration is calculated using the LS15 / IR _scale ratio.

Calibration follows the procedure of Lee et al. (Ibid.). High density polyethylene (HDPE), isotactic polypropylene (iPP), and propylene content of 20.0, 28.0, 50.0, 86.6, 92.0, and 95.8 wt% P. The ethylene-propylene copolymer with it is used as a reference material for IR _methyl / IR _scale calibration. The composition of the reference material is determined by NMR. The reference material is delivered by an SEC with an IR5 detector. The obtained IR _methyl / IR _scale ratios of the reference materials are plotted as a function of their composition to obtain a calibration curve.

The HDPE standard is used for routine LS15 calibration. The reference M _w is pre-determined by GPC as 104.2 kg / mol using an LS detector and an RI (refractive index) detector. GPC uses NBS1475 as a reference material in GPC. This reference material has a certified value of 52.0 kg / mol by NIST. Dissolve 7-10 mg of standard material in 8 mL of decan at 160 ° C. The solution is injected into the HTLC column at 100% TCB. The polymer is eluted under constant 100% TCB at 0.01 mL / min. Therefore, polymer peaks appear at the HTLC column void volume. The calibration constant Ω is determined from the total LS15 signal ( _ALS15 ) and the total IR _scale signal ( _{AIR , scale} ).

The experimental LS15 / IR _scale ratio is then converted to M _w through Ω.

As an example, three HTLC chromatograms are shown in FIG. The black chromatogram is that of comparative BCN1 (ie, CBCN1). The red chromatogram is a blend of iPP and TAFMER ™ P-0280, an ethylene / alpha-olefin copolymer product commercially available from Mitsui Chemicals. The blue chromatogram is a blend of VERSIFY ™ 2400 (a propylene-ethylene copolymer commercially available from The Dow Chemical Company) and TAFMER ™ P-0280. The broken line is a linear regression match between the chemical compositions of iPP, VERSIFY ™ 2400, and TAFMER ™ P-0280 and their elution volumes. Note that VERSIFY ™ 2400 has two peaks. The composition and elution volume of the main peak are used for linear adaptation. All three polymers have M _w in excess of 80,000 daltons.

A transmission electron microscope (TEM) is for morphological determination. The polymer film is prepared by compression molding followed by rapid cooling. The polymer is pre-melted at 190 ° C. at 1000 psi for 1 minute, then pressed at 5000 psi for 2 minutes and then quenched for 2 minutes between cooled platens (15-20 ° C.). The compression molded film is trimmed so that the cross section is collected near the core of the film. Trimmed samples are cold polished prior to staining by removing sections from the block at −60 ° C. to prevent fouling of the elastomeric phase. The cold-polished blocks are stained with the vapor phase of a 2% ruthenium tetroxide aqueous solution for 3 hours at ambient temperature. For the staining solution, 0.2 g of ruthenium (III) chloride hydrate (RuCl ₃ x H ₂ O) was weighed in a screw-type glass bottle with a lid, and 10 ml of a 5.25% sodium hypochlorite aqueous solution was spread over a wide mouth. Prepare in addition to the bottle. Place the sample in a glass bottle using a glass slide with double-sided tape. Place the slides in a jar to suspend the blocks about 1 inch above the stain solution. Using a Leica EM UC6 microtome diamond knife, at ambient temperature, sections approximately 90 nanometers thick are collected and placed on an unused TEM grid of 600 mesh for observation.

Image Recovery-TEM images are recovered by JEOL JEM-1230 operating at an acceleration voltage of 100 kV and stored in Gatan-791 and 794 digital cameras.

Xylene-soluble fractional analysis: The weighed resin is dissolved in 200 ml of o-xylene for 2 hours under reflux conditions and used. The solution is then cooled to 25 ° C. in a temperature controlled water bath to crystallize the xylene insoluble (XI) fraction. Once the solution has cooled and the insoluble fraction has precipitated from the solution, the xylene soluble (XS) fraction from the xylene insoluble fraction is separated by filtration through a filter paper. The remaining o-xylene solution is evaporated from the filtrate. Both the XS and XI fractions are dried in a vacuum oven at 100 ° C. for 60 minutes and weighed.

¹³ C Nuclear Magnetic Resonance (NMR) is related to the following.

Sample Preparation: Add approximately 2.7 g of a 50/50 mixture of 0.025 M tetrachloroethane-d2 / ortodichlorobenzene with chromium acetylacetonate (relaxant) to 0.21 g of sample in a 10 mm NMR tube. Prepare a sample by. The sample is melted and the tube and its contents are heated to 150 ° C. for homogenization.

Data acquisition parameters: Data is collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high temperature CryoProbe. The data are 320 transient signals per data file, 7.3 seconds pulse repetition delay (6 seconds delay + 1.3 seconds collection time), 90 degree flip angle, and inverse at 125 ° C sample temperature. Obtained using gated decoupling. All measurements are made on non-rotating samples in locked mode. Samples are homogenized just prior to insertion into a heated (130 ° C.) NMR sample exchanger and thermally equilibrated with a probe for 15 minutes before data acquisition.

Gel Permeation Chromatography (GPC): Gel permeation chromatography is a system consisting of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument. The column and rotary compartment are operated at 140 ° C. Three Polymer Laboratories 10-micron Mixed-B columns are used. The solvent is 1,2,4 trichlorobenzene. Samples are prepared at a concentration of 0.1 grams of polymer in 50 ml of solvent containing 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by gently stirring at 160 ° C. for 2 hours. The injection volume used is 100 μl and the flow rate is 1.0 ml / min.

21 narrow molecular weight distribution polystyrene standards with molecular weights in the range of 580-8,400,000 arranged in 6 "cocktail" mixtures with GPC column set calibrations with at least 10 separations between individual molecular weights. Use a thing. Polystyrene standards purchased from Polymer Laboratories (Shropshire, UK) in 0.025 g solvent for molecular weights of 1,000,000 or more and 50 ml solvent for molecular weights less than 1,000,000. Prepare at 0.05 g. The polystyrene standard is dissolved at 80 ° C. with gentle stirring for 30 minutes. A mixture of narrow standards is run first to reduce the highest molecular weight component and minimize degradation. The polystyrene standard peak molecular weight is converted to polyethylene molecular weight using the following equation (described in Williams and Ward, J. Polymer. Sci., Polymer. Let., 6, 621 (1968)).

Polypropylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Version 3.0.

Preparation of Block Complex A block complex is produced using a catalyst supplied to two reactors at the same time. The block composite is composed of (I) ethylene-propylene polymer, (II) isotactic propylene polymer, and (III) ethylene-propylene soft block having the same composition as ethylene-propylene polymer, and isotactic propylene polymer. Includes with block polymers containing isotactic polypropylene hard blocks of the same composition. For block copolymers, ethylene-propylene soft blocks are produced in the first reactor and isotactic propylene hard blocks are produced in the second reactor. The division ratio between the soft block and the hard block in the block copolymer is about 70/30.

The block complex is prepared using two continuous stirred tank reactors (CSTRs) connected in series and using a catalyst that is simultaneously fed to both reactors. The soft block is produced in the first reactor and the hard block is produced in the second reactor. Each reactor is hydraulically full and is set to operate under steady state conditions. In particular, block complexes are prepared by running monomers, catalysts, cocatalyst-1, cocatalyst-2, and SA (as chain shuttling agent) according to the process conditions summarized in Table 1 below. Two port injection devices are used to separately feed the catalyst, cocatalyst-1, cocatalyst-2, and SA (shutling agent) -1 to the reactor. For the preparation of the block complex, the catalyst was ([[rel-2', 2'''-[(1R, 2R) -1,2-cyclohexanediylbis (methyleneoxy-κO)]] bis [3- (9H-carbazole-9-yl) -5-methyl [1,1'-biphenyl] -2-orato-κO]] (2-)] dimethyl-hafnium). Cocatalyst-1 is a mixture of methyldi (C _14-18 alkyl) ammonium salts of tetrakis (pentafluorophenyl) borate, which is a long chain trialkylamine (Armeen ™ M2HT, Akzo-Nobel, Inc. Prepared and used by the reaction (available from.). Cocatalyst-2 is a mixture of bis (tris (pentafluorophenyl) -alman) -2-undecylimidazolide C _14-18 alkyldimethyl prepared according to Example 16 of US Pat. No. 6,395,671. It is an ammonium salt. SA is a solution of diethylzinc (DEZ) from Akzo Nobel Chemicals that may contain 1-3 mol% modified methylarmoxane (MMAO-3A). Water and / or additives may be injected into the polymer solution as soon as it exits the reactor.

The process conditions for forming the block complex are as follows.

The block composites obtained include ethylene propylene (EP) polymers, isotactic polypropylene (iPP) polymers, and EP-iPP block copolymers. The DSC melting point temperature profile of the obtained block composite is shown in FIG.

The characteristics of the block complex are shown in Table 2 below.

The block complex has a block complex index (BCI) of 0.175. The term BCI is defined herein as equal to the weight percent of a block copolymer divided by 100% (ie, weight fraction). The value of the block complex index can range from 0 to 1.0, where 1.0 is equal to 100% of the block copolymer and zero is for materials such as traditional blends or random copolymers. Is. In other words, the insoluble fraction is assigned a BCI of 1.000 and the soluble fraction is assigned a BCI of zero.

In particular, the BCI is based on showing that the polymer contains a significant amount of ethylene that would otherwise not be present in the insoluble fraction if it were simply a blend of iPP homopolymers and EP copolymers. To account for this "excess ethylene", mass balance calculations are performed to estimate the block complex index from the amount of xylene-insoluble and soluble fractions and the weight% ethylene present in each of the fractions. can do. To account for this "excess ethylene", mass balance calculations are performed to estimate the block complex index from the amount of xylene-insoluble and soluble fractions and the weight% ethylene present in each of the fractions. can do.

The sum of weight% ethylene from each fraction according to equation 1 yields total weight% ethylene (in the polymer). This mass balance equation can also be used to quantify the amount of each component in a two-component blend, or can be extended to a three-component blend or an n-component blend.

Equations 2-4 are applied to calculate the amount of soft block (providing a source of excess ethylene) present in the insoluble fraction. By substituting weight% C ₂ for the insoluble fraction on the left side of equation 2, weight% iPP hard and weight% EP soft can be calculated using equations 3 and 4. Note that the weight% of ethylene in the EP soft is set to be equal to the weight% ethylene in the xylene soluble fraction. The weight% ethylene in the iPP block is set to 0 or otherwise put that value in its position if known from the melting point of its DSC or measurements of other compositions. Can be done.

After the description of the "additional" ethylene present in the insoluble fraction, the only way to have the EP copolymer present in the insoluble fraction, the EP polymer chain, must be connected to the iPP polymer block (otherwise it is , Extracted into a xylene-soluble fraction). Therefore, when the iPP block crystallizes, it can reduce and / or prevent it from solubilizing the EP block.

Specifically, for the block complex used herein, the BCI is calculated as shown below in Table 3.

The relative quantity of each block must be taken into account in order to estimate the BCI. To approach this, the ratio between EP soft and iPP hard is used. The ratio between the EP soft polymer and the iPP hard polymer can be calculated using Equality 2 from the mass balance of total ethylene measured in the polymer. Alternatively, it can also be estimated from the mass balance of monomer and comonomer consumption during polymerization. The weight fraction of iPP hard and the weight fraction of EP soft are calculated using equation 2 and are premised on that iPP hard does not contain ethylene. EP soft weight% ethylene is the amount of ethylene present in the xylene soluble fraction.

For example, if the iPP-EP polymer is made under conditions that produce an EP soft polymer having an overall 47% by weight C ₂ and 67% by weight C ₂ and an iPP homopolymer containing no ethylene at all. The amounts of EP soft and iPP hard are 70% by weight and 30% by weight, respectively. When the percentage of EP is 70% by weight and the iPP is 30% by weight, the relative ratio of EPDM: iPP block can be expressed as 2.33: 1. Thus, if one of ordinary skill in the art performed xylene extraction of the polymer and recovered 40% by weight insoluble and 60% by weight soluble, this was an unexpected result, and this was a block copolymer fraction. It leads to the conclusion. If the ethylene content of the insoluble fraction was measured to be substantially 25% by weight C ₂ , equations 2-4 can be solved to account for this additional ethylene and also 37.3. By weight% EP soft polymer and 62.7% by weight iPP hard polymer can be present in the insoluble fraction.

Due to the error in the analytical measurements used to estimate the composition of the hard and soft blocks, as well as the estimation from the total polymer composition, a relative error of 5-10% is in the calculated value of the block complex index. It can happen. Such an estimate is made by weight% C ₂ on the iPP hard block as measured by DSC melting point, NMR analysis, or process conditions; from the xylene-soluble composition, or by NMR, or (if detected) of the soft block. Includes average weight% C _{2 in} soft blocks estimated by DSC melting point. Overall, however, the block complex index calculation reasonably explains the unexpected amount of "additional" ethylene present in the insoluble fraction and is the only one with an EP copolymer present in the insoluble fraction. Method, the EPDM polymer chain must be connected to an iPP polymer block (otherwise it is extracted into a xylene soluble fraction).

The block complex is further blended to prepare a modifier as described below.

Preparation of Modifier The modifier is a blend of block composites, high meltflow polyolefin copolymers, and additional copolymers with a refractive index that is substantially consistent with the refractive index of polypropylene.

Specifically, the materials mainly used are as follows.

[table]

The first modifier is prepared using 30% by weight block composite, 50% by weight polyolefin copolymer, and 20% by weight copolymer 1 based on the total weight of the first modifier. .. The second modifier is prepared using 30% by weight block composite, 50% by weight polyolefin copolymer, and 20% by weight copolymer 2 based on the total weight of the second modifier. ..

Specifically, the first and second modifiers are prepared by melt blending at a speed of 500 RPM with a co-rotating twin-screw extruder, 25 mm, Coperion WP-25 ZSK. Ingredients are fed to the extruder using individual loss / weight feeders. Antioxidant additives are tumble blended with the elastomer prior to compounding. The compound extruder speed is 0.38 kg / min (50 lb / hour) at a melting temperature of about 220 ° C. (430 ° F.).

Preparation of Examples and Comparative Examples For Examples, one of the first modifier and the second modifier is blended in different weight percent to form test pieces of different thicknesses. Comparative examples are prepared using benchmark polypropylene copolymers that are not blended with either of the preformed first or second modifiers.

Specifically, the materials mainly used are as follows.

[table]

Examples 1-6 and Comparative Examples A-C are prepared according to the formulations shown in Table 4 below.

Specifically, the samples of Examples 1 to 6 and Comparative Examples A to C are produced by injection molding. Specifically, the propylene base and the modifier are each dry-blended according to the formulation and injection molded by a Krauss-Maffei KM110-390 injection molding machine of B 1470C, Lab 1 in Freeport. Plaques (7.6 cm x 7.6 cm dimensions x 0.16 cm or 0.075 cm corresponding sample thickness) are made using a single mold and used for ASTM, flexural modulus, and tensile tests. A sample is cut from the plaque according to an ASTM tensile test piece.

The forms of Comparative Examples B and C and Examples 1 to 3 are shown in FIGS. 2A to 2E, respectively. Morphology is shown for both 5 μm and 1 μm. A significant improvement in domain size of Examples 1 to 3 (FIGS. 2C to 2E) is observed as compared with Comparative Examples B and C. The morphology is measured by TEM as described above.

The characteristics of Examples 1 to 6 and Comparative Examples A and B at a plaque test piece thickness of 1.60 mm are evaluated as shown in Table 5 below.

The characteristics of Examples 1 to 6 and Comparative Examples A and B at a plaque test piece thickness of 0.75 mm are evaluated as shown in Table 6 below.

With respect to Tables 5 and 6, bending test pieces, optical test pieces, and impact test pieces are cut from a 7.6 cm x 7.6 cm plaque. Properties are measured using the corresponding test methods described above.
The present invention includes the following embodiments.
[1] A composition for forming a container to be used at a temperature lower than the ambient temperature, wherein the composition is a modifier of 12% by weight to 30% by weight.
(A) A block composite of 20% by weight to 40% by weight based on the total weight of the modifier, wherein the block composite is (i) ethylene-propylene copolymer, (ii) isotactic polypropylene polymer. , And (iii) a block copolymer comprising an ethylene-propylene soft block having the same composition as the ethylene-propylene polymer and an isotactic polypropylene hard block having the same composition as the isotactic polypropylene polymer, wherein the soft block Contains 50% to 80% by weight of ethylene based on the total weight of the soft blocks, and the block copolymer comprises 20% to 50% by weight of the hard blocks based on the total weight of the block copolymers. , Block composites, including block copolymers,
(B) A 40% to 60% by weight polyolefin copolymer based on the total weight of the modifier, derived from at least one of ethylene and C _{3 to} C ₁₀ alpha-olefins at 190 ° C./ according ASTM D 1238 at 2.16 kg, 100 g / 10 min ~1500g / 10 min melt index, and 0.860 g ^/ cm 3 having a density of ~0.900g / cm ^3, a polyolefin copolymer, and
(C) Of the first additional copolymer, optionally 0% to 30% by weight, having a refractive index of 1.490 to 1.510, and a second additional copolymer that is miscible with polypropylene. At least one, the second additional copolymer is derived from at least one of propylene and ethylene and butene, at least one of the first additional copolymer and the second additional copolymer. With modifiers, including
A composition comprising a 70% to 88% by weight propylene polymer base having a melt flow rate of 2 g / 10 min to 100 g / 10 min according to ASTM D 1238 at 230 ° C./2.16 kg.
[2] The composition according to the above [1], wherein the propylene polymer base contains the random copolymer polypropylene having an ethylene content of 0.5% by weight to 5.0% by weight based on the total weight of the random copolymer polypropylene. Stuff.
[3] The composition according to [1] or [2] above, wherein the block complex has a melt flow rate of 2 g / 10 min to 100 g / 10 min according to ASTM D1238 at 230 ° C./2.16 kg. ..
[4] A form in which the block composite of the modifier, the polyolefin copolymer, and optionally an additional copolymer of the modifier are pre-blended prior to mixing the modifier with the propylene polymer base. The composition according to any one of [1] to [3] above, wherein the composition comprises a modifier finely dispersed in the polypropylene polymer.
[5] The first additional copolymer is present in an amount of 10% to 30% by weight, the block composite is present in an amount of 25% to 35% by weight, and the polyolefin elastomer is present in an amount of 45% by weight to 45% by weight. The composition according to any one of the above [1] to [4], which is present in an amount of 55% by weight.
[6] The first additional copolymer is a copolymer derived from at least two selected from ethylene, propylene, butylene, pentene, hexene, heptene, and octene, and the first additional copolymer is a copolymer. The composition according to the above [5], which is a styrene-based copolymer.
[7] The composition according to any one of the above [1] to [6], wherein the polyolefin elastomer is derived from octene.
[8] The composition according to any one of the above [1] to [7], wherein the modifier is present in an amount exceeding 15% by weight.
[9] A freezer container formed from the composition according to any one of the above [1] to [8], wherein the film formed from the composition is prepared according to ASTM D256 at −20 ° C. A freezer container with a thickness of less than 3.0 mm, a transparency of more than 98%, and an Izod impact of more than 5 kJ / m ² .
[10] A method for producing a composition for forming a container to be used at a temperature lower than the ambient temperature.
(A) A block copolymer of 20% by weight to 40% by weight based on the total weight of the modifier, wherein the block copolymer contains an isotactic polypropylene hard block and an ethylene-propylene soft block, and the soft block. Contains 50% to 80% by weight ethylene based on the total weight of the soft block, and the block copolymer comprises 20% to 50% by weight of the hard block based on the total weight of the hard copolymer. , Block copolymers,
(B) 40% to 60% by weight of polyolefin elastomer based on the total weight of the modifier, the polyolefin elastomer from 100 g / 10 min to 100 g / 10 min according to ASTM D1238 at 190 ° C./2.16 kg. A polyolefin elastomer having a melt index of 1500 g / 10 min and a density of 0.860 g / cm ^{3 to} 0.900 g / cm ³ and said that the polyolefin elastomer is derived from at least one C _{3 to} C ₁₀ alpha-olefin. When,
(C) To prepare the modifier, which is a blend of 0% to 30% by weight of any copolymer having a refractive index of 1.490 to 1.510.
Blending with 12% to 30% by weight of the modifier and 70% to 88% by weight of the propylene polymer base, wherein the propylene polymer base is ASTM D 1238 at 230 ° C./2.16 kg. According to the method, which has a melt flow rate of 2 g / 10 min to 100 g / 10 min.

Claims (10)

A composition for forming a container to be used at a temperature lower than 0 ° C. , wherein the composition is a modifier of 12% by weight to 30% by weight.
(A) A block composite of 20% by weight to 40% by weight based on the total weight of the modifier, and the block composite is (i) an ethylene-propylene copolymer and (ii) an isotactic polypropylene polymer. , and (iii) the ethylene - propylene soft block multiblock copolymer containing isotactic polypropylene hard block composed of the same monomer and and said isotactic polypropylene polymer, - propylene copolymer to be composed of the same monomer ethylene The soft block contains 50% by weight to 80% by weight of ethylene based on the total weight of the soft block, and the multi- block copolymer contains 20% by weight to 50% by weight based on the total weight of the multi- block copolymer. Block composites, including multi- block copolymers, including the hard blocks by weight%.
(B) A 40% to 60% by weight polyolefin copolymer based on the total weight of the modifier, derived from at least one of ethylene and C _{3 to} C ₁₀ alpha-olefins at 190 ° C./ according ASTM D 1238 at 2.16 kg, 100 g / 10 min ~1500g / 10 min melt index, and 0.860 g ^/ cm 3 having a density of ~0.900g / cm ^3, a polyolefin copolymer, and (c) 0 Ru least 1 Tsudea of butene interpolymers - for wt% to 30 wt%, the first additional copolymer having a refractive index of 1.490 to 1.510, and propylene - ethylene interpolymer and a propylene - ethylene With a modifier, including at least one of the second additional copolymers ,
A composition comprising a 70% to 88% by weight propylene polymer base having a melt flow rate of 2 g / 10 min to 100 g / 10 min according to ASTM D 1238 at 230 ° C./2.16 kg. The composition of claim 1, wherein the propylene polymer base comprises said random copolymer polypropylene having an ethylene content of 0.5% to 5.0% by weight based on the total weight of the random copolymer polypropylene. The composition of claim 1 or 2, wherein the block composite has a melt flow rate of 2 g / 10 min to 100 g / 10 min according to ASTM D1238 at 230 ° C./2.16 kg. Wherein said block composite modifier, said polyolefin copolymer,及Beauty, copolymers of additional said modifier is provided the modifying agent in pre-blended form prior to mixing with the propylene polymer base, The composition according to any one of claims 1 to 3, wherein the composition contains a modifier finely dispersed in the polypropylene polymer. The first additional copolymer is present in an amount of 10% to 30% by weight, the block composite is present in an amount of 25% to 35% by weight, and the polyolefin elastomer is present in an amount of 45% to 55% by weight. The composition according to any one of claims 1 to 4, which is present in an amount of. It said first additional copolymers, ethylene, propylene, butylene, pentene, hexene, heptene, and copolymers der Luca derived from at least two selected from octene, or, the first additional copolymer The composition according to claim 5, which is a styrene-based copolymer. The composition according to any one of claims 1 to 6, wherein the polyolefin elastomer is derived from octene. The composition according to any one of claims 1 to 7, wherein the modifier is present in an amount exceeding 15% by weight. A freezer container formed from the composition according to any one of claims 1 to 8, wherein the film formed from the composition is less than 3.0 mm at −20 ° C. according to ASTM D256. A freezer container with a thickness of more than 98% transparency and an Izod impact of more than 5 kJ / m ² . A method for producing a composition for forming a container to be used at a temperature lower than 0 ° C.
(A) A 20% to 40% by weight multi- block copolymer based on the total weight of the modifier, wherein the multi- block copolymer comprises an isotactic polypropylene hard block and an ethylene-propylene soft block. The soft block contains 50% to 80% by weight of ethylene based on the total weight of the soft block, and the multi- block copolymer contains 20% to 50% by weight of the hard based on the total weight of the hard copolymer. With multi- block copolymers, including blocks,
(B) 40% to 60% by weight of polyolefin elastomer based on the total weight of the modifier, the polyolefin elastomer from 100 g / 10 min to 100 g / 10 min according to ASTM D1238 at 190 ° C./2.16 kg. A polyolefin elastomer having a melt index of 1500 g / 10 min and a density of 0.860 g / cm ^{3 to} 0.900 g / cm ³ and said that the polyolefin elastomer is derived from at least one C _{3 to} C ₁₀ alpha-olefin. When,
(C) 0% by weight to 30% by weight of the copolymer having a refractive index of 1.490 to 1.510, and to prepare the modifier is a blend of
Blending with 12% to 30% by weight of the modifier and 70% to 88% by weight of the propylene polymer base, wherein the propylene polymer base is ASTM D 1238 at 230 ° C./2.16 kg. According to the method, which has a melt flow rate of 2 g / 10 min to 100 g / 10 min.